N-(3,4,4-trifluorobutene-3)thiazalodine dione

ABSTRACT

Compounds of the formula

United States Patent Brokke June 24, 1975 N-(3,4,4-TRIFLUOROBUTENE- 3)THIAZALODINE DIONE [56] References Cited [75] Inventor: Mervin E. Brokke, Moraga, Calif. UNITED STATES PATENTS [73] Assigneez Smufi-er Chemical p y 3,780,050 12/1973 Brokke 260/306 es port Conn Primary Examiner-Richard J. Gallagher Filed! P 27, 1973 Attorney, Agent, or Firm-Harry A. Pacini; Daniel C. [211 pp Nu: 355 254 BlOCk; Edwin H. Baker Related US. Application Data Division of Serr No. 208,032, Dec 8 l97l, Pat. No. 3.780.050. which is a division of Ser' No 877,538 Nov. 20. 1969. Pat No. 3.691536 which is a division of Serl No 490,664, Sept. 27 l965. Pat. No. $513,172

US. Cl 260/306.7 R Int. Cl C07d 91/16 Field of Search 260/3067, 306.7 R

phthalimido, and N-thiazolidyl dione. The compounds are useful as nematocides.

1 Claim, No Drawings 1 N-(3,4,4-TRIFLUOROBUTENE-3)THIAZALODINE DIONE This application is a division of copending application Ser. No. 208,032 filed Dec. 8, 1971 now US. Pat. No. 3,780,050 issued Dec. 18, 1973 which in turn is a divisional application of then copending application Ser. No. 877,538, filed Nov. 20, 1969 now US. Pat. No. 3,697,536 issued Oct. 10, 1972 which in turn is a divisional application of then copending application Ser. No. 490,664, filed Sept. 27, 1965 now US. Pat. No. 3,513,172, issued May 19, 1970.

This invention relates to certain new and novel chemical compounds and to the utility of said compounds as effective nematocides. More specifically, this invention relates to compounds of the general formula wherein R is a member selected from the group consisting of chlorothiophenyl, thio-3,4,4-trifluoro-3-butenyl, 2-thio-4,4,6trimethyldihydropyrimidyl, 2-thiobenzoxazoyl, 2-thiobenzothiazolyl, 2-thio-4-alkylthiazolyl, S- (3 ,4,4-trifluoro-3-butenyl )-ethylene-bis(dithiocarbamoyl), thiobenzyl, thionaphthyl, phthalimido, dithio- 3,4,4-trifluoro-3-buteny1, thiopyridyl, N-thiazolidyl dione, and 5-thio-3-phenyl-1,2,4-thiadiazolyl.

The compounds herein contemplated can be prepared by various methods. One such general method of preparing the compound with bonding by means of a thio group is the condensation of the appropriate thiol (R-Sl-l) and 3,4,4-trifluoro-3-butenyl bromide, usually in the presence of an organic base, such as triethylamine. Similarly, compounds wherein bonding is through a heterocyclic nitrogen condensation is accomplished using the appropriate sodium or potassium salt of the heterocyclic nitrogen containing compound and 3,4,4-trifluoro-3-butenyl bromide. The reactions proceed readily in the liquid phase. The employment of an inert organic solvent is also useful, facilitating processing as well as agitation of the reactants. Temperatures that permit operation in the liquid phase and which are between room temperature and reflux temperature of the solvent, if one is used, are employed. Preferably the reaction mixture is refluxed, usually at an elevated temperature.

[t has been found that the compounds of the present invention are particularly effective as nematocides. They are effective in the control of nematodes when applied to a nematodal habitat.

The compounds of the present invention may be prepared in accordance with the following illustrative examples.

EXAMPLE 1 Preparation of p-chlorophenyl 3,4,4-trifluoro-3-butenyl sulfide 1n 200 ml. methanol was dissolved 14.4 g. of pchlorothiophenol. To this solution was added 25 g. of 25 percent sodium methoxide followed by 18.9 g. of 3,- 4,4-trifluoro-l-bromobutene-3. The resulting mixture was stirred and heated under reflux for 1 hour. The solvent was removed in vacuo. The residue was taken up in benzene, washed with water and dried over anhydrous magnesium sulfate. The benzene was evaporated. There was obtained 19.3 g. of the title compound, n 1.5360.

EXAMPLE 2 Preparation of Bis(3,4,4-trifluoro-3-butenyl) ethylene-bis(dithiocarbamate) Ethylene diamine (0.2 moles) and triethylamine (0.2 moles) were dissolved in ml. of dioxane. Carbon disulfide (0.2 moles) was added dropwise with stirring at l020C. Stirred at room temperature for 15 minutes after addition was completed, then heated to 40C. for 15 minutes. To the reaction mixture was added 0.15 mole (28.4 g.) of 3,4,4-trifluoro-3-butenyl bromide. This was heated to 60C. for 2 hours. The reaction mixture was poured into water and extracted with benzene. The benzene solution was subsequently washed with water, dried over anhydrous calcium chloride and tinally the benzene removed in vacuo. There was obtained 77.4 g. of the title compound, n 1.5292.

EXAMPLE 3 Preparation of 3-Phenyl-5 3 ,4,4-trifluoro-3-butenylthia)-1,2,4- thiadiazole 3-Phenyl-1,2,4-thiadiazole thiol-5, 6.6 g., were mixed with 9.5 g. of 3,4,4-trifluoro-3-butenyl bromide in cc. of dioxane as a solvent with 10.1 g. of triethylamine as the catalyst. The reaction mixture was refluxed for 2% hours. Isolation of the title compound was in the same manner as in Example 2. There was obtained 8.8 g. ofa dark oil, n 1.5687.

EXAMPLE 4 Preparation of N-( 3,4,4-trifluoro-3-butenyl) 2,4-thiazolidenedione In 100 ml. of methanol there was dissolved l 1.7 g. of 2,4-thiazolidinedione. This was treated with 0.1 mole of sodium methoxide in methanol. To this solution was added 18.9 g. of 3,4,4-trifluoro-3-butenyl bromide. The resulting mixture was refluxed for 2 hours. The solvent was then evaporated and the residue was taken up in benzene. The benzene solution was washed with water, dried over anhydrous calcium chloride, and the solvent evaporated. There was obtained 7.2 g. of the title compound, m?" 1.4578. Analysis of the infrared spectrum supported the proposed structure.

As previously mentioned, the herein described novel compositions produced in the above described manner are biologically active compounds which are useful and valuable in the control of various organisms. The compounds of the invention were tested as nematocides in the following manner.

NEMATOCIDE EVALUATION TEST This test determines a candidates action on root-knot nematodes (Meloidogyne, sp.) in soil. One-pound portions of soil infested with root-knot nematodes were placed in quart jars. The chemical to be tested was pipetted into the nematode-infested soil at various dilutions of from 55 to 1 part per million (ppm) or until activity was lost. After mixing the candidate compound into the soil, the soil was sealed for 48 hours. The treated soil was then placed in paper containers and allowed to stand in a greenhouse 1 week for airing. At the end of this time a tomato plant was transplanted into the soil. The root-knot nematodes attack the tomato plant roots if they survived the chemical treatment, and cause swelling or knots on the roots. Four weeks after treatment, the plant was removed from the soil and the roots inspected. The lowest concentration which prevented nematode development was recorded.

The following table is a listing of the compounds prepound of the present invention is as a spray, drench or dust followed by incorporation.

Various changes and modifications may be made pared according to the aforedescribed procedures. Col- 5 without departing from the spirit and scope of the inumn II is the results obtained from the nematocide vention described herein as will be apparent to those evaluation test. The values given in Column ll are conskilled in the art to which it pertains. [t is accordingly centrations (ppm) which allowed no nematode develintended that the present invention shall only be limopment. ited by the scope of the appended claim.

TABLE Column l Column ll Nematode COMPOUND n Control (ppm) p-chlorophenyl 3,4,4-trifluoro-3-butenyl sulfide 1.5 360 so bis(3,4,4-trifluoro-3-butenyl) sulfide l.4087 2.5 2-(3,4,4-trifluoro-3-butenyllhio)-4,4,6-

trimethyldihydropyrimidine l.4949 25 2-( 3,4,4-trifluoro-3-butenylthio benzoxazole l.5385 (2.5) 2-( 3,4.4-trifluoro-3-butenylthic )'benzot 'azo l.5863 (2.5) 2-(3,4,4-trifluoro-3-butenylthio)-4- methylthiazole LSBSS (l) bis( 3,4,4-trifluoro-3-bulenyl) ethylenebis( dithiocarbamute) L5292 l 0) phenyl 3,4,4-trifluoro-3-butenyl sulfide l.5442 50 3-phenyl-5-( 3 ,4,4-trifluoro-3-bute nylthia)-l ,2.4-thiadiazole l.5687 (2.5) 3,4.4-trifluoro-3-butenyl benzyl sulfide l.$l 3,4.4-trifluoro-3-butenyl ci-naphthyl sulfide LSSOS (50) N-( 3.4.4-trifluoro-3-butenyl )phthullmide (semi-solid) (2.5) bis( 3,4.4-trlfluoro-3-butenyl) disulfide (liquid) (2.5) 2-( 3,4.4-trlfluoro-3-butenylthio pyri ne l.5258 25 4-( 3,4,4-trifluoro-B-butenylthio)- pyridine 1.547! (2.5) N-(3.4.4-trifluoro-3-butenyl) 2,4-

thlnclidenedione l .4678 l partial control The compounds of the present invention may be used What is claimed is: as effective nematocides and may be applied in a varil. The compound of the formula ety of ways at various concentrations. In practice, the compounds are usually formulated with an inert nematocidal adjuvant, utilizing methods well-known to those skilled in the art, thereby making them suitable for application as dusts, sprays, or drenches. The amount ap- CF CFCH Gl'i 2 2 2 p ted will depend upon the nature of the nematode to V be controlled and the rate of application may vary from i l to pounds per acre. One particularly advantageous way of applying the nematocidal composition comprising the adjuvant and an effective amount of a comp p 

1. THE COMPOUND OF THE FORMULA 